Multibed cartridge for ion exchange



Oct. 10, 1950 I... MONFRIED uuurman CARTRIDGE FOR ION EXCHANGE Filed July 12, 1946 x 7 5 J! v J. 1 H w a. e a H. W41. rm 0 M 2 Patented Oct. 10, 1950 Leon Monfried, New York, N.:Y., assimor its American Cyanamld Company, New York, N. Y., a corporation oi. Maine Application July 12, 1946, Serial No. 683,263

Claims. (Cl. 206-46) This invention relates to packages of ion exchange materials and more particularly, to packages the containers of which may be partially or wholly constructed of laminated materials including especially paper laminae or may be partially or wholly constructed of single ply materials such as sheet metal, molded plastic sheets, and the like.

The packages of my invention comprise cation 7 active materials and anion active materials packed in alternate layers in a container so as to permit uniform passage of a liquid through the container whereby the cation active materials and the anion active materials purify and demineralize the liquid by removing ionizable substances.

Previously, water and other liquids have been purified by passing them through beds of cation active materials and anion active materials but these purification systems have involved the use of heavy equipment including metallic, porcelain, or wooden tanks of considerable size.

There has been a demand for a highly purified water of a quality comparable to distilled water in many places where stills are not available or where it would be difficult to transport the stills or other equipment normally used for the purification of water by means of ion active materials. Furthermore, there has been a demand for a light, portable water purification unit, particularly for use in connection with military operations, which may be used, for example, to treat brackish water in order that it may be useful for motor vehicle radiators, for drinking, for cooking or for any other such purpose which does not demand the degree of purity of distilled water.

Previously, a lightweight container adapted to contain ion active materials and to permit a substantially uniform passage of a fluid such as water through the container has been devised. This container has a plurality of compartments separated by foraminous members, top and bottom covers, each of said covers having an inlet or an outlet, and foraminous members at the top of the top compartment and at the bottom of the bottom compartment, said members spaced a substantial distance from the top and bottom covers, respectively.

I have developed an improved ion exchange package which comprises a practicable and economically feasible improvement in the container referred to in the foregoing paragraph.

According to the present invention a container comprising a top cover provided with a hole, a

2 top foraminous member held a substantial'distance apart from said cover, a bottom cover with a hole and a bottom foraminous member held a substantial distance apart from said bottom cover, is filled with alternate layers of cation active and anion active materials. These layers are packed between the top and bottom forammg air during transportation orstorage.

inous members sufliciently tightly to prevent mixing of the said cation and anion active'material layers.

I The accompanying drawing illustrates my invention and reference thereto will clarify its description.

The figure is a central ,vertical section of my material package showing stoppers placed in the holes of the covers of the container, which stoppers carry conduits to permit the flow of liquid into and out of said container.

Container I has a cylindrical wall 2,13, top cover 3, and a bottom cover 4. Top and bottom covers 3 and 4 contain holes 5 and 6, respectively. The covers are preferably made of metal and attached to the wall 2 of container 1 by crimping the edges thereof over the top and bottom peripheries of the wall 2.

A dish-shaped spacer I which is preferably constructed of molded plastic is inverted and arranged so that the edges thereof are in contact with the top cover 3. The spacer 1, which is provided with relatively large openings 8, is contiguous to a liquid-permeable member 9 which may be a screen. Dish-shaped spacer In, similar in construction to spacer l, is inverted and arranged so that its edges are supported by the bottom cover 4. The top surface of the spacer III, which is provided with relatively large openings II, supports a foraminous member l2.

Alternate layers Of granular anion active material l3 and i5, and also indicated A in the drawing, and of granular cation active materials I4 and I6, also indicated 0 in the drawing, are packed in the container between the top and bottom foraminous members 9 and 12. It is preferable that the anion active material l3 be an especially treated or buffered anion active material treated so that water flowing from the container will have a. controlled pH between 6and 8. I

Prior to use, holes 5 and 6 are preferably closed with a suitable cover in order to preserve the condition, of the ion active materials by exclud- For this reason, metallic tops or covers which are always completely vapor-proof are preferred a1- though the tops may be of adhesive paper, ad-' hesive tape, etc.v

When the package is to be used in a liquid purification process; the temporary covers are removed from the holes 5 and 8. Conduit I! is inserted in hole 5 in the top 'cover 3 and secured in place and made fluid tight by means of a'plug or stopper l8 through which conduit l1 passes. Similarly, a conduit I9 is inserted in hole 6 in the bottom cover 4 and secured in place and made fluid tight by means of a plug or stopper 2!) through which conduit I9 passes. The liquid to be purified, such as water, flows 7 in through conduit l9 and into the space between the bottom cover 4 and the spacer Ill. The liquidthen passes through the spacer l and is so distributed thereby that it flows uniformly through the foraminous means I I, thence through the cation active material I6, through the anion active material l5, through the cation active material l4, through the anion active material 13 which may be especially treated as mentioned above in order to control the pH of the efiiuent, through the liquid-permeable member 9, through the openings 8 of the spacer I into the space between the top cover 3 and the spacer I, and finally out through conduit l1.

The-foregoing description and the drawing to which it refers relate to a package which contains four layers of ion exchange materials, alternately anion and cation. The invention is in no sense limited t a package containing any particular number of layers of ion exchange materials nor must there be an even number of alternate layers. While, in general, I have found most practicable a package containing four, six or eight layers of alternate cation and anion active materials, and these therefore constitute the preferred embodiment of my invention,

packages containing more or fewer layers are.

also contemplated. For example, an eminently satisfactorily functioning package, particularly if the liquid to be purified contains silica, may comprise five layers, four of them of alternate cation and anion exchange materials and the fifth of an anion exchange material which may or may not be specially activated.

My package is adapted for the passage of liquid to be purified in either direction, but it is preferable that the liquid flows in the bottom and out the top. Since it is generally preferable that a liquid to be demineralized be passed through a bed of cation active material first and through a bed of anion active material last regardless of whether or not the last anion bed he buffered, the liquid should be introduced into that end of the container where the cation active material is placed. In order to avoid the possibility of the liquid being introduced into the wrong end of the container I prefer to make the holes 5 and 6 of different sizes and, in general, I prefer that the hole 6 in the bottom cover 4 be larger than hole 5 in the top cover 3. However, this is merely a matter of preference and the reverse procedure may be employed is desired.

My container may be made of any suitable material such as sheet metal, plastic, or laminated materials including those comprising paper laminae. If metals be employed it is preferable that the metal be such as will withstand the high acidity and basicity which occurs during the use of the cartridge in the purification of water and other fluids in the various compartments filled with ion active materials. If a corrodable metal is used, it is preferable that the inside surface thereofbe coated with a water-proof,

acid-proof and alkali -proof composition such as pitch from still residues of petroleumor coal origin either :alone or with a drying oil, rubber, polystyrene, copolymers of vinyliden'e. chloride andvinyl chloride (such as those sold under the trade name Saran) etc. A container constructed of metal has many advantagesincluding superior strength, better appearance, adaptability to lithographic marking, and the like.

.The container, aswell as the covers thereof, may be molded of plastic, either with or without filler or reinforcing material. Thus, for example, the outside wall of the container may be constructed of cloth or paper bonded together with a plastic such as a urea-formaldehyde resin, an alkylated urea-formaldehyde resin, a phenolformaldehyde resin, a melamine-formaldehyde resin, an alkylated melamine-formaldehyde resin, polystyrene, a hard rubber, a copolymer of unsaturated substances such as a copolymer of an unsaturated alkyd resin with styrene or an allyl ester, a polymer of an unsaturated substance such as polyallyl esters, an acrylonitrile polymer, etc., or it may be constructed of plastic alone. Fillers which may be used in conjunction with these resins include: cellulosic fibers, asbestos fibers, synthetic poly-amide fibers (such as those sold under the trade name "Nylon), glass fibers, wood flour, etc. If the container is made of laminated sheets, these may be woven of paperlike materials and may include one or more of the fibers mentioned above.

Inasmuch as the present container may be discarded after use, it is preferable that the container be made of as cheap materials as possible. Lightweight materials are also highly desirable for obvious reasons. Accordingly, it is often preferable that the container be constructed of a laminated material including paper laminae and, if so, that it be suitably water-proofed. For water-proofing, any of the materials mentioned above as suitable for coating corrodable metals may be used. Furthermore, metal foil may be included in the laminated material in order to improve the water resistance of the material without adding greatly to the weight of the material.

Other laminated materials than those described above, such as laminated paper impregnated with paraffin, bituminous and asphaltic substances, synthetic resins, etc., may be used for the wall of my containers, as indicated previously.

My containers may be square, elliptical, or circular in cross-section. It is generally preferable that they be cylindrical, chiefly because of the resultant simplicity of manufacture.

It is important that the top and bottom foraminous members each be held a substantial distance from the top and bottom covers, respectively, in order to obtain uniform flow through the container without channeling. Accordingly, it is preferable that the distance between the top and bottom covers and the adjacent foraminous members be at least inch and more'particularly, that this distance be between about a; of the smallest diameter of the container and about t; of the largest diameter of the container. In general, the largest and smallest diameters are intended to represent the largest and smallest dimensions of a cross-section of any particularly shaped container. Of course, if the container is circular, the largest and smallest diameters are the same.

Any cation active material may be. used in the appropriate layers of my containers. The cation active materials should be used in the hydrogen activated form when they are said to be operated on the "hydrogen cycle or described as "hydrogen active" since they exchange hydrogen ion in the purification process. Examples oi' suitable cation active materials, which may be used 'are polyhydric phenol-aldehyde condensation products, catechol tannin-formaldehyde condensation products, aromatic sulphonic acid-formaldehyde condensation products (as described in U. S. Patent No: 2,204,539), the carbonaceous materials such as coal, peat, lignite, etc., the insolubilized alpha-furyl sulphonates, furfuralmineral acid halide condensation products as described in the copending application of James R. Dudley, Serial No. 528,768, filed March 30, 1944, now matured into U. S. Patent No. 2,408,615, sulfonated or phosphonated resinified furfural as described in the copending application of Jack T. Thurston, Serial No. 652,235,fi1ed March 5, 1946, aldehyde condensation products of sulfonated hydroxy aromatic compounds containing activating groups such as ketone groups as described in the copending application of Jack T. Thurston, Serial No. 541,480, filed June 21, 1944, now matured into U. S. Patent No. 2,440,669, etc.

Cation active materials may be activated before placing in my containers by treatment with dilute acid solution, e. g., 01-10% of hydrochloric acid, sulphuric acid, etc., and subsequently washing the material with water to remove free acid.

Any anion active resin may be used in the appropriate layers of my containers and among these, some examples are: the aldehyde condensation products of m-phenylene diamine, biguanide, guanyl urea, substituted guanidines such as methyl guanidine, substituted biguanides such as phenyl-biguanide, or polyamines preferably polyethylene polyamines, etc. Such condensation products are preferably formaldehyde condensation products, although other aldehyde condensation products may be used if desired. Examples of other aldehydes which may be used are: furfural, acrolein, benzaldehyde, etc. The active resins, such as those prepared from guanidine, guanyl urea, biguanide or other materials which do not form sufliciently insoluble condensation products with formaldehyde for most practical purposes, are preferably insolubilized with one or more suitable formaldehyde reactive materials, e. g., urea, thiourea, or the amonotriazines (especially melamine and the guanamines which react with formaldehyde to produce insoluble products), etc. The anion active resins prepared from guanidine, guanyl urea, or biguanide, etc., may be prepared in the general manner described in U. S. Patents No. 2,251,234 and 2,285,750.

Other anion active resins which may be used include condensation products with polyalkylene polyamines of acetalciehyde and formaldehyde as described in the copending application of Jack T. Thurston, Serial No. 643,836, filed January 26, 1946, now abandoned, or acrylonitrile-ammonocarbonic acid adducts such as described in the copending application of James R. Dudley, Serial No. 653,175, filed March 1, 1946, now matured into U. S. Patent No. 2,445,735, or of crotonaldehyde and formaldehyde as described in the copending application of James R. Dudley, Serial No. 643,838, filed January 26, 1946, now abandoned. Similarly, condensation products of epichlorhydrin and polyamines as described in the copending application of James R. Dudley and Lennart A. Lundberg, Serial No. 616,644, filed September 15, 1945, now matured into U. S. Patent No. 2,469,683, of polyepoxy compounds and polyamines as described in the copending application of James R. Dudley, Serial No. 655,005,

-'filed March 16, 1946, now matured into U. S.

Patent No. 2,469,684, of glycerol dichlorhydrin and polyamines as described in the copending application of Lennart A. Lundberg, Serial No. 624,606, filed October 25, 1945, now matured into U. S. Patent No, 2,469,693, or of polyacrylic acid and polyamines as described in the copending application of James R.-Dudley, Serial No. 648,818, filed February 19, 1946, aldehyde condensation products of furyl aliphatic amines as described in the copending application of James R. Dudley, Serial No. 642,416, filed January 19, 1946, etc., may be used.

The anion active resin employed in the first anion layer is preferably activated in the conventional manner by treatment with a dilute solution of an alkaline material, e. g], a 01-10% solution of sodium hydroxide, sodium carbonate or of a corresponding potassium salt, etc. A buffered anion active material may, if desired, be used in which case it constitutes the last layer of anion active material. Such a material is first activated in the conventional manner and is then treated with a reagent to buffer it to a desired point. In other words, a reagent is selected which will give to an aqueous solution or to water flowing from the container a desired pH. If a substantially neutral product be desired, the anion active resin in compartment 13 may be adjusted or buffered so that the pH of the efiluent will be about 7.5 or between 6 and 8 by treating the resin with sufllcient carbon dioxide in the presence of water or by treating the resin with a dilute solution of sodium bicarbonate mixed with sodium hydroxide or sodium carbonate.

I claim:

1. A package which consists of a container comprising a top cover provided with a hole, a top foraminous member held a substantial distance apart from said to cover, a bottom cover with a hole and a bottom foraminous member held a substantial distance apart from said bottom cover, and a plurality of layers of cation active materials and anion active materials packed between the top and bottom foraminous members sufilciently tightly to prevent mixing of said cation and anion active materials, said container being adapted to permit the uniform passage of a liquid tobe demineralized through said cation active and anion active materials.

2. A package which consists of a container comprising a top cover provided with a hole, a top foraminous member held a substantial distance apart from said topcover, a bottom cover with a. hole and a bottom foraminous member held a substantial distance apart from said bottom cover, and alternate layers of cation active' materials and anion active materials packed between the top and bottom foraminous members sufllciently tightly to prevent mixing of said cation and anion active materials, said container being adapted to permit the uniform passage of a. liquid to be demineralizedthrough said cation active and anion active materials.

3. A package which consists of a tubular container comprising a top cover provided 'with a hole, a top foraminous member held a substantial distance apart from said top cover, a bottom cover with a hole and a bottom foraminous member held a substantial distance apart from said bottom cover, and at least four alternate layers of cation active materials and anion active materials packed between the top and bottom foraminous members sufliciently tightly to prevent mixing of said cation and anion active materials, said container being adapted to permit the uniform passage of a liquid to be demineralized through said cation and anion active material layers.

4. A package which consists of a tubular container comprising a top cover provided with a hole, a top foraminous member held a substantial distance apart from said top cover, a bottom cover with a hole and a bottom foraminous member held a substantial distance apart from said bottom cover, and from about four to eight alternate layers of cation active materials and anion active materials packed between the top and bottom foraminous members sufllciently tightly to prevent mixing of said cation and anion active materials, said container being adapted to permit the uniform passage of a liquid to be demineralized through said cation and'anion active material layers.

5. A package which consists of a tubular con- Number Name Date 1,267,327 McCarty May 21, 1918 v 2,087,157 Lind July 13, 1937 2,404,367 Durant et a1 July 23, 1946 2,423,224 a Card July 1, 1947 tainer comprising a top cover provided with a hole, a top foraminous member held a. substantial distance apart from said top cover, a bottom sage of a liquid to be demineralized through said cation and anion active material layers.

A LEON MONFRIED.

REFERENCES CITED The following references are of record in the file of this patent;

UNITED STATES PATENTS OTHER REFERENCES Angewandte Chemie of 1939, No. 11, pp. 215- 219, Griesbach; Uber die Herstellung und Anwendung neuerer Austauschadsorbentien." 

3. A PACKAGE WHICH CONSISTS OF A TUBULAR CONTAINER COMPRISING A TOP COVER PROVIDED WITH A HOLE, A TOP FORAMINOUS MEMBER HELD A SUBSTANTIAL DISTANCE APART FROM SAID TOP COVER, A BOTTOM COVER WITH A HOLE AND A BOTTOM FORAMINOUS MEMBER HELD A SUBSTANTIAL DISTANCE APART FROM SAID BOTTOM COVER, AND AT LEAST FOUR ALTERNATE LAYERS OF CATION ACTIVE MATERIALS AND ANION ACTIVE MATERIALS PACKED BETWEEN THE TOP AND BOTTOM FORAMINOUS MEMBERS SUFFICIENTLY TIGHTLY TO PREVENT MIXING OF SAID CATION AND ANION ACTIVE MATERIALS, SAID CONTAINER BEING ADAPTED TO PERMIT THE UNIFORM PASSAGE OF A LIQUID TO BE DEMINERALIZED THROUGH SAID CATION AND ANION ACTIVE MATERIAL LAYERS. 